Utilization of hazardous materials in oil based mud waste to turn - PowerPoint PPT Presentation

Utilization of hazardous materials in oil based mud waste to turn into value added polymeric nanocomposite materials Shohel Ahmed Siddique, Urenna V Adegbotolu, Kyari Yates, James Njuguna E ‐ mail: s.a.siddique@rgu.ac.uk, Tel: +44(0)1224 262310

Outline • Background • Aim & objectives • Methodology • Analysis • Results discussion • Conclusion

Background Existing oil based mud (OBM) waste treatment methods  Physical treatment  Chemical process  Biological process  Thermal treatment Fig. 1: The circulation of drilling mud during the drilling of an oil well. Source: https://www.britannica.com/technology/drilling ‐ mud

Existing OBM waste management options (based on cost, time, efficiency) Treatment Time Cost * (AUS$) Advantages Disadvantages Composting 56 ‐ 8 days 60 ‐ 80 useful by ‐ product air emission, fire risk 200 ‐ 800 Land farming days 10 ‐ 12 low cost Environmental pollution 400 ‐ 1200 Land treatment days 4 ‐ 5 low cost long ‐ term monitoring Bio augmented 100 ‐ 200 landfarming days 15 ‐ 20 low cost intense monitoring needed 500 ‐ 3000 Burial pit days 10 ‐ 12 on site treatment long term monitoring needed 300 ‐ 2500 long term monitoring needed; legislative issues; Landfills days 40 ‐ 60 relatively low cost slow biodegradaing rates 10 ‐ 30 large cost; expertise needed; maintenance Bio reactors days 700 rapid process issues 28 ‐ 56 Vermiculture days 80 ‐ 100 useful by ‐ product suitable for a limited range of pollutants Chemical solidification/sta 1 ‐ 2 100 ‐ 250 (plus large set ‐ up cost; risk associated with long term bilisation tonnes/h disposal costs) rapid process stabilisation 5 ‐ 6 large set ‐ up and running cost; may not remove Incineration tonnes/h 500 ‐ 1000 waste reduction all pollutants Thermal 3 ‐ 10 waste reduction and desorption tonnes/h 400 ‐ 1500 low retention time large set ‐ up and running cost; Source: Ball AS, Stewart RJ, Schliephake K. A review of the current options for the treatment and safe disposal of drill cuttings. Waste Manag Res 2012 May; 30(5) :457 ‐ 473.

Thermomechanical Cuttings Cleaner (TCC) Sustainable solution ??? Fig. 2: Diagram of TCC system Source: http://www.halliburton.com/en ‐ US/ps/baroid/fluid ‐ services/waste ‐ management ‐ solutions/waste ‐ treatment ‐ and ‐ disposal/thermal ‐ processing ‐ systems/thermomechanical ‐ cuttings ‐ cleaner ‐ tcc.page

OBM waste composition as a hazardous material List I and II pollutants in environment *: Hazardous waste classified in according to Directive 2008/98/EC Fig. 3: Percentage of individual chemical constituents present in OBM and WBM discharge adapted from Hudgins . Source: Siddique S, Kwoffie L, Addae ‐ Afoakwa K, Yates K, Njuguna J. Oil Based Drilling Fluid Waste: An Overview on Environmentally Persistent Pollutants. In IOP Conference Series: Materials Science and Engineering 2017 May (Vol. 195, No. 1, p. 012008). IOP Publishing.

Aim and Objectives Aim: To understand and evaluate the crystallinity and thermal degradation behaviour of PA6 nanocomposites using reclaimed clay from oil based drilling fluids waste. Objectives 1. Morphology investigation of PA6/OBMFs nanocomposites using SEM. 2. Elemental analysis of PA6/OBMFs nanocomposites using EDXA. 3. Chemical structure analysis using FTIR technique. 4. PA6/OBMFs nancomposites decomposition study using TGA. 5. Degradation study of PA6/OBMFs nancomposites using DSC.

Methodology Materials and experiments  Matrix material Characterisation • PA6  Nanofiller • OBMFs (Thermally treated) SEM Manufacturing Process EDXA FTIR TGA DSC Fig. 4: Schematic representation of (a) PA6/ OBMFs nanocomposite manufacturing process and (b) different experimental analysis of PA6/ OBMFs nanocomposite.

SEM analysis (c) (a) (b) (d) (e) Fig. 5: SEM images of (a) PA6; (b) PA6 with 2.5 wt% OBMFs; (c) PA6 with 5.0 wt% OBMFs; (d) PA6 with 7.5 wt% OBMFs; and (e) PA6 with 10.0 wt% OBMFs.

EDXA analysis (a) (b) (c) (d) (e) (f) Fig. 6: EDX spectra of (a) OBMFs; (b) PA6; (c) PA6+2.5 wt% OBMFs; (d) PA6+5.0 wt% OBMFs; (e) PA6+7.5 wt% OBMFs and (f) PA6+10.0 wt% OBMFs.

FTIR analysis: Fig. 7: Comparison of FTIR full scale spectra of PA6 and its nanocomposite.

ATR FT ‐ IR peak assignments Wave number (cm ‐ 1 ) Assignments 3295 Hydrogen ‐ bonded N ‐ H stretching 3079 Fermi ‐ resonance of N ‐ H stretching 2930 V as (CH 2) 2859 V s (CH2) 1633 Amide I 1539 Amide II 1462 CH 2 deformation 1435 CH 2 deformation 1370 Amide III & CH 2 wag 1259 Amide III & CH 2 wag 1200 Amide III & CH 2 wag 1169 CO ‐ NH, skeletal motion (Am) 1118 C ‐ C stretching (Am) 1074 C ‐ C stretch (Am) 973 CO ‐ NH in plane vibration 680 Amide V 525 ‐ 580 Primary aliphatic nitriles (C Ξ N)

Decomposition behaviour of PA6 and its nanocomposite Fig. 8: TGA of PA6 and PA6/OBMFs nanocomposites at: (a) complete thermograms of all samples; (b) 250°C; (c) D ½; (d) 600 °c.

TGA analysis at different decomposition stages of PA6 and its nanocomposites % wt loss at D 1/2 Residue (% wt) Material 250 °C T D10% (° c) T D50% (° c) Time at 600 °C PA6 3.37 399.24 431.42 40.82 0.00 PA6+2.5 wt% OBMFs 2.93 407.77 442.23 41.61 2.03 PA6+5.0 wt% 42.42 OBMFs 2.87 416.87 446.21 6.79 PA6+7.5 wt% OBMFs 3.19 412.32 439.38 41.35 7.59 PA6+10.0 wt% 416.87 447.35 OBMFs 2.65 42.27 6.09

Degradation behaviour of PA6 and its nanocomposite Fig. 9: DSC thermograms of PA6 and its nanocomposites at (a) Tg ; (b) T m and (c) T c .

% of crystallinity calculation % crystallinity= [ ∆ Hm - ∆ Hc]/ ∆ Hm 0 * 100% Material ∆ Hm (J/g) ∆ Hc(J/g) ∆ Hm ‐∆ Hc(J/g) (( ∆ Hm ‐∆ Hc)/ ∆ Hm°) *100% PA6 52.83 0 52.83 22.96 PA6+2.5 wt% OBMFs 48.05 0 48.05 20.88 PA6+5.0 wt% OBMFs 49.32 0 49.32 21.43 PA6+7.5 wt% OBMFs 51.56 0 51.56 22.41 PA6+10.0 wt% OBMFs 50.73 0 50.73 22.05

Heat Capacity Calculation C p = ( δ Q/ δ t ) x ( δ t/ δ T ) Mass of samples Heat Specific heat capacity (Cp) Jk ‐ 1 kg ‐ 1 Material (m) mg capacity (J/g) PA6 6.20 60.57 2523 PA6+2.5 wt% OBMFs 6.30 55.87 2327 PA6+5.0 wt% OBMFs 6.30 57.66 2402 2522 PA6+7.5 wt% OBMFs 7.80 60.55 1321 PA6+10.0 wt% OBMFs 6.30 64.69

Schematic diagram of RAF and MAF Fig. 10: Schematic diagram of OBMFs platelets associated with MAF and RIF of PA6 matrix

RAF and MAF Calculation MAF= ( ∆ Cp/ ∆ Cp(am)) *100% RAF= 1 ‐ crystallinity ‐ ∆ C p / ∆ C p pure RAF’= 1 ‐ filler content ‐ ∆ C p / ∆ C p pure or CF Ꞌ RAF= 100 ‐ MAF ‐ CF RAF Ꞌ = 100 ‐ MAF ‐ CF Ꞌ Material MAF CF TIF PA6 27.26 22.96 0.00 49.78 72.74 72.74 PA6+2.5 wt% OBMFs 27.46 20.88 2.50 51.66 70.04 72.54 PA6+5.0 wt% OBMFs 58.91 21.43 5.00 19.66 36.09 41.09 PA6+7.5 wt% OBMFs 46.01 22.41 7.50 31.58 46.49 53.99 PA6+10.0 wt% OBMFs 55.04 22.05 10.00 22.91 34.96 44.96

Relation between TIF and filler dispersion Fig. 11: Relation between TIF and dispersion behaviour of OBMFs in PA6 matrix

Conclusion • In TGA, the % weight loss of PA6/OBMFs nanocomposites decreases with the incremental weight % of OBMFs in PA6/OBMFS nanocomposites • There is not any significant heat capacity property changes for PA6 with 2.5 wt%, 5.0 wt% and 7.5 wt% OBMFs nanocomposites • There is a drastically heat capacity (about 47%) reduction noticeable for PA6 with 10.0 wt% nanocomposite • 50% TIF line deduce the degree of dispersity in PA6/OBMFs nanocomposites

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